U.S. patent number 9,073,951 [Application Number 13/575,345] was granted by the patent office on 2015-07-07 for method of preparing an organohalosilane.
This patent grant is currently assigned to Dow Corning Corporation. The grantee listed for this patent is Kurt E. Anderson, Aswini K. Dash, Charles Alan Hall, Dimitris Katsoulis, Robert Thomas Larsen, Matthew J. McLaughlin, Jonathan David Wineland. Invention is credited to Kurt E. Anderson, Aswini K. Dash, Charles Alan Hall, Dimitris Katsoulis, Robert Thomas Larsen, Matthew J. McLaughlin, Jonathan David Wineland.
United States Patent |
9,073,951 |
Anderson , et al. |
July 7, 2015 |
Method of preparing an organohalosilane
Abstract
A method of preparing organohalosilanes comprising combining an
organohalide having the formula RX (I), wherein R is a hydrocarbyl
group having 1 to 10 carbon atoms and X is fluoro, chloro, bromo,
or iodo, with a contact mass comprising at least 2% (w/w) of a
palladium suicide of the formula Pd.sub.xSi.sub.y (II), wherein x
is an integer from 1 to 5 and y is 1 to 8, or a platinum suicide of
formula Pt.sub.zSi (III), wherein z is 1 or 2, in a reactor at a
temperature from 250 to 700.degree. C. to form an
organohalosilane.
Inventors: |
Anderson; Kurt E. (Crestwood,
KY), Dash; Aswini K. (Florence, KY), Hall; Charles
Alan (Crestwood, KY), Katsoulis; Dimitris (Midland,
MI), Larsen; Robert Thomas (Midland, MI), McLaughlin;
Matthew J. (Midland, MI), Wineland; Jonathan David
(Bedford, KY) |
Applicant: |
Name |
City |
State |
Country |
Type |
Anderson; Kurt E.
Dash; Aswini K.
Hall; Charles Alan
Katsoulis; Dimitris
Larsen; Robert Thomas
McLaughlin; Matthew J.
Wineland; Jonathan David |
Crestwood
Florence
Crestwood
Midland
Midland
Midland
Bedford |
KY
KY
KY
MI
MI
MI
KY |
US
US
US
US
US
US
US |
|
|
Assignee: |
Dow Corning Corporation
(Midland, MI)
|
Family
ID: |
44320064 |
Appl.
No.: |
13/575,345 |
Filed: |
January 24, 2011 |
PCT
Filed: |
January 24, 2011 |
PCT No.: |
PCT/US2011/022195 |
371(c)(1),(2),(4) Date: |
July 26, 2012 |
PCT
Pub. No.: |
WO2011/094140 |
PCT
Pub. Date: |
August 04, 2011 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20120289730 A1 |
Nov 15, 2012 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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61298375 |
Jan 26, 2010 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07F
7/16 (20130101) |
Current International
Class: |
C07F
7/12 (20060101) |
Field of
Search: |
;556/478,472,450
;502/178,185 |
References Cited
[Referenced By]
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Feb 1953 |
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JP |
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JP |
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JP |
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0248034 |
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Jun 2002 |
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WO |
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WO |
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WO |
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2014028417 |
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WO |
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2014062255 |
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Apr 2014 |
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WO |
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Other References
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|
Primary Examiner: Katakam; Sudhakar
Assistant Examiner: Bakshi; Pancham
Attorney, Agent or Firm: Brown; Catherine U. Fewkes; Matthew
T.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a U.S. national stage filing under 35 U.S.C.
.sctn.371 of PCT Application No. PCT/US11/022,195 filed on Jan. 24,
2011, currently pending, which claims the benefit of U.S.
Provisional Patent Application No. 61/298,375 filed Jan. 26, 2010
under 35 U.S.C. .sctn.119 (e). PCT Application No.
PCT/US11/022,195, U.S. Provisional Patent Application No.
61/298,375 are hereby incorporated by reference.
Claims
That which is claimed is:
1. A method of preparing an organohalosilane, the method
comprising: combining an organohalide having the formula RX (I),
wherein R is a hydrocarbyl group having 1 to 10 carbon atoms and X
is fluoro, chloro, bromo, or iodo, with a contact mass comprising
at least 2% (w/w) of a palladium silicide of the formula
Pd.sub.xSi.sub.y (II), wherein x is an integer from 1 to 5 and y is
an integer 1 to 8, or a platinum silicide of formula Pt.sub.zSi
(III), wherein z is 1 or 2, in a reactor at a temperature from 250
to 750.degree. C. to form an organohalosilane.
2. The method of claim 1, wherein the hydrocarbyl group has 1 to 6
carbon atoms and X is chloro.
3. The method of claim 1, wherein the organohalide is methyl
chloride, methyl bromide, or methyl iodide.
4. The method of claim 1, wherein the contact mass comprises at
least 90% (w/w) of a silicide selected from PdSi, Pd.sub.2Si,
Pd.sub.3Si, Pd.sub.5Si, Pd.sub.2Si.sub.8, PtSi, and Pt.sub.2Si.
5. The method of claim 1, wherein the silicide is selected from
PdSi, Pd.sub.2Si, Pd.sub.2Si.sub.8 and PtSi.
6. The method of claim 1, wherein the reactor is selected from a
fluidized bed reactor, a vibrating bed reactor, and a stirred bed
reactor.
7. The method of claim 1, wherein the organohalosilane has the
formula R.sub.aSiX.sub.4-a, wherein each R is independently H or a
hydrocarbyl group having 1 to 10 carbon atoms; X is fluoro, chloro,
bromo, or iodo; and a is an integer from 1 to 3.
8. The method of claim 7, wherein R is methyl and X is chloro.
9. The method of claim 1, further comprising recovering the
organohalosilane.
10. The method of claim 1, further comprising replenishing the
reactor with a zero-valent silicon or contact mass after the
organohalosilane has been produced.
11. The method of claim 1, wherein the contact mass comprises
essentially no zero-valent silicon.
12. The method of claim 1, wherein the temperature is from 250 to
700.degree. C.
13. The method of claim 1, further comprising pre-heating and
gasifying the organohalide before combining with the contact
mass.
14. The method of claim 1, further comprising pre-heating the
contact mass in an inert atmosphere and at a temperature up to
700.degree. C. prior to combining with the organohalide.
15. A method of preparing a polysiloxane, the method comprising
hydrolyzing the organosilane produced according to the method of
claim 1.
Description
FIELD OF THE INVENTION
The present invention relates to a method of preparing an
organohalosilane, comprising combining an organohalide having the
formula RX (I) with a contact mass to form an organohalosilane,
wherein R is a hydrocarbyl group, X is a halo group, and the
contact mass comprises at least 2% (w/w) of a palladium or platinum
silicide.
BACKGROUND OF THE INVENTION
Methods of preparing organohalosilanes are known in the art.
Typically, organohalosilanes are produced commercially by the
Mueller-Rochow Direct Process, which comprises passing an
organohalide over zero-valent silicon in the presence of a copper
catalyst and various optional promotors. A mixture of
organohalosilanes, the most important of which is
dimethyldichlorosilane, are produced by the Direct Process.
The typical process for making the zero-valent silicon used in the
Direct Process consists of the carbothermic reduction of SiO.sub.2
in an electric arc furnace. Extremely high temperatures are
required to reduce the SiO.sub.2, so the process is very energy
intensive. Consequently, production of zero-valent silicon adds
costs to the Direct Process for producing organohalosilanes.
Therefore, there is a need for a more economical method of
producing organohalosilanes that avoids or reduces the need of
using zero-valent silicon.
BRIEF SUMMARY OF THE INVENTION
The present invention is directed to a method of preparing an
organohalosilane, the method comprising combining an organohalide
having the formula RX (I), wherein R is a hydrocarbyl group having
1 to 10 carbon atoms and X is fluoro, chloro, bromo, or iodo, with
a contact mass comprising at least 2% (w/w) of a palladium silicide
of the formula Pd.sub.xSi.sub.y (II), wherein x is an integer from
1 to 5 and y is and integer from 1 to 8, or a platinum silicide of
formula Pt.sub.zSi (III), wherein z is 1 or 2, in a reactor at a
temperature from 250 to 700.degree. C. to form an
organohalosilane.
The method of the present invention produces an organohalosilane
from a silicon source other than zero-valent silicon. The
organohalosilane produced by the present method is the precursor of
many products in the silicone industry. For example, the
organohalosilane is the precursor used to make many silicone fluids
and resins.
DETAILED DESCRIPTION OF THE INVENTION
As used herein, the term "a" or "an" means one or more.
As used herein, "integer" means a natural number and zero.
As used herein, the meaning of "combine," "combined," and
"combining" is intended to include, but is not limited to, the
meaning "to cause to react or unite."
A method of preparing an organohalosilane, comprising:
combining an organohalide having the formula RX (I), wherein R is a
hydrocarbyl group having 1 to 10 carbon atoms and X is fluoro,
chloro, bromo, or iodo, with a contact mass comprising at least 2%
(w/w) of a palladium silicide of the formula Pd.sub.xSi.sub.y (II),
wherein x is an integer from 1 to 5 and y is and integer from 1 to
8, or a platinum silicide of formula Pt.sub.zSi (III), wherein z is
1 or 2, in a reactor at a temperature from 250 to 700.degree. C. to
form an organohalosilane.
The organohalide has the formula RX (I), wherein R is hydrocarbyl
group having 1 to 10 carbon atoms and X is fluoro, chloro, bromo,
or iodo.
The hydrocarbyl groups represented by R in formula (I) typically
have from 1 to 10 carbon atoms, alternatively from 1 to 6 carbon
atoms, alternatively from 1 to 4 carbon atoms. Acyclic hydrocarbyl
groups containing at least three carbon atoms can have a branched
or unbranched structure. Examples of hydrocarbyl groups include,
but are not limited to, alkyl, such as methyl, ethyl, propyl,
1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl,
1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl,
2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl,
2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl;
cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl;
aryl, such as phenyl and naphthyl; alkaryl, such as tolyl, and
xylyl; aralkyl such as benzyl and phenylethyl; alkenyl, such as
vinyl, allyl, and propenyl; aralkenyl, such as styryl and cinnamyl;
and alkynyl, such as ethynyl and propynyl.
Examples of organohalides include, but are not limited to, methyl
chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl
bromide, ethyl iodide, chlorobenzene, bromobenzene, iodobenzene,
vinyl chloride, vinyl bromide, vinyl iodide, allyl chloride, allyl
bromide, and ally iodide.
Methods of preparing organohalides are well known in the art; many
of these compounds are commercially available.
The contact mass comprises at least 2% (w/w), alternatively at
least 25% (w/w), alternatively at least 50% (w/w), alternatively at
least 75% (w/w), alternativley at least 90% (w/w), alternatively at
least 95% (w/w), alternatively about 100% (w/w), based on the total
weight of the contact mass, of a palladium silicide of the formula
Pd.sub.xSi (II), wherein x is an integer from 1 to 5, or a platinum
silicide of formula Pt.sub.zSi (III), wherein z is 1 or 2.
The palladium silicide has the formula Pd.sub.xSi.sub.y (II),
wherein x is an integer from 1 to 5, alternatively x is 1, 2, 3, or
5, alternatively x is 1 or 2, alternatively x is 2, and y is and
integer from 1 to 8, alternatively y is 1 when x is 1, 3, 4, or 5
and y is 1 or 8 when x is 2; alternatively y is 1.
Examples of palladium silicides include, but are not limited to,
PdSi, Pd.sub.2Si, Pd.sub.3Si, Pd.sub.5Si, and Pd.sub.2Si.sub.8. The
palladium silicide may be a single palladium silicide or a mixture
of palladium silicides, each having the formula (II).
Palladium silicides may be made by methods well known in the art.
For example, the methods disclosed in U.S. Pat. No. 3,297,403 and
US 2009/0275466 may be used. The palladium silicide may be obtained
commercially from, for example, Alfa Aesar and ACI Alloy.
The platinum silicide has the formula Pt.sub.zSi (III), wherein z
is 1 or 2. Examples of platinum silicides include PtSi and
Pt.sub.2Si. The platinum silicide may be a single platinum silicide
or a mixture of PtSi and Pt.sub.2Si.
Platinum silicides may be made by methods well known in the art as
described above for the palladium silicide. The platinum silicide
may be obtained commercially from, for example, Alfa Aesar and ACI
Alloy.
The contact mass may comprise a mixture of palladium silicides, a
mixture of platinum silicides or a mixture of palladium and
platinum silicides. For example, the contact mass may be a mixture
of PdSi and Pd.sub.2Si or of Pt.sub.2Si and PtSi.
The contact mass may further comprise up to 98% (w/w),
alternatively up to 75% w/w), alternatively up to 50% (w/w),
alternatively up to 25% (w/w), alternatively up to 10% (w/w),
alternatively up to 5% (w/w), based on the total weight of the
contact mass, zero-valent silicon. In a another embodiment, the
contact mass comprises essentially no zero-valent silicon. As used
herein, "essentially no zero-valent silicon" is intended to mean
that there is no zero-valent silicon other than at the level of an
impurity. For example, essentially no zero-valent silicon means
that there is from 0 to 1% (w/w), alternatively 0 to 0.5% (w/w),
alternatively 0% (w/w), based on the total weight of the contact
mass, zero-valent silicon.
The zero-valent silicon is typically chemical or metallurgical
grade silicon; however, different grades of silicon, such as solar
or electronic grade silicon may be used. Chemical and metallurgical
grades of silicon are known in the art and can be defined by the
silicon content. For example, chemical and metallurgical grades of
silicon typically comprise at least 98.5% (w/w) silicon. Chemical
and metallurgical grades of silicon may also contain additional
elements as described below for the contact mass. Methods of making
zero-valent silicon are known in the art. These grades of silicon
are available commercially.
The contact mass may comprise other elements such as Fe, Ca, Ti,
Mn, Zn, Sn, Al, Pb, Bi, Sb, Ni, Cr, Co, and Cd and their compounds.
Each of these elements are typically present at from 0.0005 to 0.6%
(w/w) based upon the total weight of the contact mass.
The contact mass may be a variety of forms, shapes and sizes, up to
several centimeters in diameter, but the contact mass is typically
finely-divided. Finely divided, as used herein, is intended to mean
that the contact mass is in the form of a powder.
The contact mass may be produced by standard methods for producing
particulate silicon from bulk silicon, such as silicon ingots. For
example, attrition, impact, crushing, grinding, abrasion, milling,
or chemical methods may be used. Grinding is typical. The contact
mass may be further classified as to particle size distribution by
means of, for example, screening or by the use of mechanical
aerodynamic classifiers such as a rotating classifier.
If the contact mass comprises more than a single silicide, for
example if the contact mass comprises at least two silicides or a
silicide and zero-valent silicon, these components typically are
mixed. The mixing may be accomplished by standard techniques known
in the art for mixing solid particles. For example, the mixing may
be accomplished by stirring or shaking. Further, mixing may be
accomplished in the processing to produce the contact mass particle
size mass distribution as described and exemplified above. For
example, mixing may be accomplished in a grinding process. Still
further, the mixing may be accomplished during the production of
the palladium silicide or platinum silicide. For example, PdSi and
Pd.sub.2Si may be formed and mixed in the process combining molten
silicon with molten palladium.
The method of the invention can be carried out in a suitable
reactor for conducting the Direct Process. For example, a sealed
tube, an open tube, a fixed bed, a stirred bed, and a fluidized bed
reactor may be used.
The organohalide and contact mass are typically combined by
charging the reactor with the contact mass followed by flowing the
gaseous organohalide through the contact mass; however, the reactor
may be first charged with the organohalide followed by introduction
of the contact mass.
The rate of addition of the organohalide to the contact mass is not
critical; however, when using a fluidized bed, the organohalide is
introduced into the reactor bed at a rate sufficient to fluidize
the bed but below a rate that will completely elutriate the bed.
The rate will depend upon the particle size mass distribution of
the particles in the bed and the dimensions of the fluidized bed
reactor. One skilled in the art would know how to determine a
sufficient rate of organohalide addition to fluidize the bed while
not completely elutriating the material from the bed. When not
using a fluidized bed, the rate at which the organohalide is added
to the bed is typically selected to optimize contact mass
reactivity.
The method may further comprise combining the organohalide and
contact mass in the presence of an inter gas. For example, an inert
gas may be added with the organohalide to the contact mass.
Examples of the inert gas that may be introduced with the
organohalide include nitrogen, helium, argon and mixtures
thereof.
The method may be conducted with agitation of the reactants.
Agitation may be accomplished by methods known in the art for
catalyzed reactions between gases and solids. For example, reaction
agitation may be accomplished within a fluidized bed reactor, in a
stirred bed reactor, a vibrating bed reactor and the like. However,
the method may be conducted without agitation of the reactants by,
for example, flowing the alkyl halide as a gas over a packed bed
comprising the palladium or platinum silicide.
The method may be carried out at atmospheric pressure conditions,
or slightly above atmospheric pressure conditions, or elevated
pressure conditions may be used.
The temperature at which the contact mass and organohalide are
combined is from 250 to 750.degree. C., alternatively 280 to
700.degree. C., alternatively 300 to 700.degree. C., alternatively
from 400 to 700.degree. C. The temperature at which the contact
mass and organohalide are combined influences the selectivity of
the method for producing monoorganohalosilane or
diorganohalosilane. The selectivity may be determine by gas
chromatography as defined in the examples section, or through other
suitable analytical techniques.
The contact mass and organohalide are typically combined for
sufficient time to form organohalosilanes from the reaction of the
palladium or platinum silicide with the organohalide. For example,
in a batch-type reactor, the contact mass and organohalide are
typically combined from 5 minutes to 24 h, alternatively from 1 to
7 h, alternatively from 4 to 7 h, at a temperature from 300 to
700.degree. C. In a continuous or semi-continuous process, where
additional contact mass may be added to the reactor, and
organohalide gas is continuously passed through the contact mass,
the contact time is typically from a fraction of a second up to 30
seconds, alternatively from 0.01 to 15 seconds, alternatively from
0.05 to 5 seconds. As used herein, "contact time" is intended to
mean the residence time of gas to pass through the reactor.
When the organohalide is a liquid or solid, the method may further
comprise pre-heating and gasifying the organohalide before it is
introduced into the reactor.
The method may further comprise pre-heating the contact mass in an
inert atmosphere and at a temperature up to 700.degree. C.,
alternatively up to 400.degree. C., alternatively 280 to
525.degree. C., prior to contacting with the organohalide.
The method may further comprise introducing additional contact mass
or zero-valent silicon into the reactor to replace the silicon that
has reacted with the organohalide to form organohalosilanes.
The method may further comprise recovering the organohalosilane
produced. The organohalosilane may be recovered by, for example,
removing gaseous organohalosilane from the reactor followed by
condensation. The organohalosilane may be recovered and a mixture
of organohalosilanes separated by distillation.
The organohalosilanes prepared according to the present method
typically have the formula R.sub.aSiX.sub.4-a, wherein each R is
independently H or as described and exemplified above for the
organohalide and X is as described and exemplified above for the
organohalide, and the subscript "a" is an integer from 1 to 3.
Examples of organohalosilanes prepared according to the present
method include, but are not limited to, dimethyldichlorosilane
(i.e., (CH.sub.3).sub.2SiCl.sub.2), dimethyldibromosilane,
diethyldichlorosilane, diethyldibromosilane, trimethylchlorosilane
(i.e., (CH.sub.3).sub.3SiCl), methyltrichlorosilane (i.e.,
(CH.sub.3)SiCl.sub.3), phenyltrichlorosilane,
diphenyldichlorosilane, triphenylchlorosilane, and
methylhydrodichlorsilane (i.e., (CH.sub.3)HSiCl.sub.2. The method
may also produce small amounts of halosilane and organosilane
products such as tetramethylsilane, trichlorosilane, and
tetrachlorosilane.
The method of the present invention produces organohalosilanes from
a silicon source other than zero-valent silicon, does not require
the addition of copper as catalyst, and produces commercially
desirable organohalosilanes in good yield and proportion to less
desirable silanes.
The organohalosilanes produced by the present method are the
precursors of most of the products in the silicone industry. For
example, dimethyldichlorosilane may be hydrolyzed to produce linear
and cyclic polydimethylsiloxanes. Other organohalosilanes produced
by the method may also be used to make other silicon-containing
materials such as silicone resins or sold into a variety of
industries and applications.
EXAMPLES
The following examples are presented to better illustrate the
method of the present invention, but are not to be considered as
limiting the invention, which is delineated in the appended claims.
Unless otherwise noted, all parts and percentages are reported in
the examples are by weight. The following methods and materials
were employed in the examples:
The reaction products were analyzed by gas chromatography-mass
spectrometry using a Agilent Technologies 6890N Network GC system
with 5975B inert XL EI/CI MSD (GC-MS) to determine selectivity.
Concentration of silicon and other elements were determined by
inductively coupled plasma--atomic emission spectrometry (ICP-AES).
The method was a typical procedure known for elemental analysis of
solid samples, wherein the solids were dissolved in HF and the
concentration in aqueous solution determined with respect to
appropriate standards containing known amounts of any elements of
interest.
Methyl iodide (99+%), deuterated-methyl iodide (99+%), and methyl
bromide (99+%) are available from Sigma-Aldirch (Milwaukee, Wis.).
Methyl chloride (>99.9% (w/w) purity is available from Airgas.
The palladium and platinum silicides are available from Alfa Aesar
(Ward Hill, Mass.) and ACI Alloy (San Jose, Calif.).
The flow-through, metal reactor tube set-up consisted of a 0.25
inch stainless steel tube placed either vertically or horizontally.
The silicide to be tested was positioned in the middle of the tube,
and the organohalide was introduced from the top end of the
vertically aligned tube and from one of the ends of the
horizontally aligned tubes. The product and unreacted organohalide
were removed from the end of the tube opposite the organohalide
introduction and passed through a cold trap at -78.degree. C. The
organohalide is fed to the reactor from a gas cylinder via a mass
controller.
Silicon Conversion is the starting weight of silicon before
reaction minus the weight of silicon remaining after the reaction
divided by the starting weight of the silicon before the reaction
multiplied by 100.
As used herein, "h" is the abbreviation for hour or hours, "g" is
the abbreviation for gram or grams, "mg" is the abbreviation for
milligram or milligrams, "min" is the abbreviation for minute or
minutes, "mL" is the abbreviation for milliliters, and ".mu.L" is
the notation for microliters.
Example 1
A thick-wall glass reactor tube was charged with a sample of PdSi
(110 mg) and methyl iodide (75 .mu.L) at 23.degree. C. The tube was
evacuated at -196.degree. C., sealed and then warmed to room
temperature. The tube was than placed in an oven at 300.degree. C.
After 2 h, the temperature of the reactor tube was allowed to reach
23.degree. C. and then was frozen with liquid nitrogen
(-196.degree. C.). Using a triangular file, the tube was cut,
warmed to room temperature and then a liquid sample was collected
for analysis. The sample was injected directly for analysis by gas
chromatography-mass spectrometry and showed the selective formation
of MeSiI.sub.3 as the only organohalosilane.
Example 2
A thick-wall glass reactor tube was charged with a sample of PdSi
(110 mg) and methyl iodide (75 .mu.L) at 23.degree. C. The tube was
evacuated at -196.degree. C., sealed and then warmed to room
temperature. The tube was kept in an oven and heated at 300.degree.
C. After 5 h, the temperature of the reactor tube was allowed to
cool to 23.degree. C. and then was frozen with liquid nitrogen
(-196.degree. C.). Using a triangular file, the tube was cut,
warmed to room temperature and then a sample of the liquid product
was collected for analysis. The sample was injected directly for
analysis by gas chromatography-mass spectrometry and showed the
selective formation of the organohalosilanes MeSiI.sub.3 and
Me.sub.2SiI.sub.2. A trace amount of SiI.sub.4 was also detected.
The selectivity among organohalosilanes observed was MeSiI.sub.3
(72% (w/w)), Me.sub.2SiI.sub.2 (26% (w/w)) and SiI.sub.4 (2%
(w/w)).
Example 3
An open-ended, glass tube was loaded with 500 mg of PdSi. The tube
was heated to 330.degree. C. with an aluminum heating block. MeBr
was pumped through the tube for 7 h. Reaction products were
collected in a cold trap downstream of the tube. Headspace gas
chromatography-mass spectrometry analysis was performed on the vial
containing the liquid collected. The major products were
Me.sub.2SiBr.sub.2 and MeSiBr.sub.3. A number of other
organohalosilanes and siloxanes were seen in small amounts.
Example 4
A sample of PdSi (2.018 g) was loaded into a glass reactor tube and
pretreated with argon overnight. Next, MeCl (6 mL/min) was flowed
through the PdSi at from 200-500.degree. C. for 2.5 h, and the
product stream was analyzed by online GC. At 300.degree. C., the
product stream contained 50/50% (w/w) SiCl.sub.4/MeSiCl.sub.3; at
400.degree. C., the product stream contained 50/50% (w/w)
SiCl.sub.4/Me.sub.2SiCl.sub.2; and at 500.degree. C., and the
product stream contained 80/10/10% (w/w)
MeSiCl.sub.3/SiCl.sub.4/Me.sub.2SiCl.sub.2.
Example 5
A sample of PdSi (150.0 mg) was loaded into the flow-through, metal
reactor and pretreated with nitrogen at 150.degree. C. overnight.
Next, MeCl (30 mL/min) was flowed through the PdSi at 400.degree.
C. for 7 h. The remaining solids left in the tube were analyzed by
ICP-AES and showed Si conversion of 35% (w/w). The products were
analyzed by GC and found to contain Me.sub.2SiCl.sub.2 (31% (w/w)),
MeSiCl.sub.3 (58% (w/w)), and SiCl.sub.4 (11% (w/w)).
Example 6
A sample of Pd.sub.2Si (200.0 mg) was loaded into a flow-through,
metal reactor and pretreated with nitrogen at 150.degree. C.
overnight. Next, MeCl (30 mL/min) was flowed through the catalyst
bed continuously at 400.degree. C. for 4 h, 450.degree. C. for 1.5
h, and 500.degree. C. for 2 h. The remaining solids left in the
tube were analyzed by ICP-AES, and the Si conversion was determined
to be 82.8% (w/w). MeSiCl.sub.3 was the only organohalosilane in
the product as measured by GC.
Example 7
PtSi (0.5 g) was loaded in a flow-through, metal reactor and
pretreated with nitrogen at 150.degree. C. overnight. Next, MeCl
(30 mL/min) was flowed through the catalyst bed at 500.degree. C.
for 2 h. GC analysis showed the product formed comprised
Me.sub.2SiCl.sub.2 and MeSiCl.sub.3.
Example 8
A sample of Pd.sub.3Si (500.0 mg) was loaded into the flow-through,
metal reactor and pretreated with nitrogen at 150.degree. C.
overnight. Next, MeCl (30 mL/min) was flowed through the Pd.sub.3Si
bed and the evolution of products at 400-700.degree. C. were
analyzed by combination of GC and GC-MS techniques. No volatile
organohalosilane products were observed at 400-600.degree. C. At
700.degree. C., product comprising SiCl.sub.4 (68%) and
MeSiCl.sub.3 (31%) was produced. The reaction was continued at
700.degree. C. for another 30 min resulting in product comprising
SiCl.sub.4 (97%) and MeSiCl.sub.3 (3%).
Example 9
A sample of Pd.sub.5Si (500.0 mg) was loaded into the flow-through,
metal reactor and pretreated with nitrogen at 150.degree. C.
overnight. Next, MeCl (30 mL/min) was flowed through the Pd.sub.5Si
bed varying the temperature from 400 to 700.degree. C., and the
products were analyzed by GC and GC-MS. No volatile
organohalosilane products were observed at 400-500.degree. C. At
600.degree. C., SiCl.sub.4 (62%) and MeSiCl.sub.3 (38%) were
observed. After 30 min at 700.degree. C., product comprising
SiCl.sub.4 (77%) and MeSiCl.sub.3 (23%) was produced; and after 60
min at 700.degree. C., product comprising SiCl.sub.4 (97%) and
MeSiCl.sub.3 (3%) was produced.
Example 10
A sample of Pd.sub.2Si.sub.8 (0.51 g) was loaded into the
flow-through, metal reactor. MeCl was flowed through the
Pd.sub.2Si.sub.8 bed at 400.degree. C. and 500.degree. C., and the
products were analyzed by GC and GC-MS. At 400.degree. C., 9.5%
(w/w) Me.sub.2SiCl.sub.2, 59.3% (w/w) MeSiCl.sub.3, and 30.4% (w/w)
SiCl.sub.4 were produced, and at 500.degree. C., 2.1%
MeHSiCl.sub.2, 1.7% Me.sub.2SiCl.sub.2, 29.2% MeSiCl.sub.3, 0.5%
HSiCl.sub.3, 66.2% SiCl.sub.4, with the balance being other
silanes, were produced.
Example 11
A sample of PdSi and zero-valent Si, at a weight ratio of PdSi to
zero-valent Si of 1:22, was loaded into a flow-through, metal
reactor. MeCl was flowed through at a temperature of 400.degree. C.
for 24 hr. The products leaving the reactor were analyzed by GC and
GC-MS after 6 and 24 hr. After 6 hours, 76% (w/w) MeHSiCl.sub.2, 4%
(w/w) Me.sub.2SiCl.sub.2, 17% (w/w) MeSiCl.sub.3 were produced, and
62% (w/w) MeHSiCl.sub.2, and 16% (w/w) Me.sub.2SiCl.sub.2 after 24
hr, with the balance being other silanes, were produced. The total
Si conversion was 2.4%.
Example 12
A sample of PdSi (500.0 mg) was loaded into a flow-through, metal
reactor and treated with nitrogen at 150.degree. C. overnight.
Next, MeCl (30 mL/min) was flowed through the PdSi bed at
400.degree. C. for 2 h. The products were analyzed by GC and found
to contain Me.sub.2SiCl.sub.2 (73.5% (w/w)), and MeSiCl.sub.3
(26.5% (w/w)).
Example 13
A sample of PdSi (500.0 mg) was loaded into a flow-through, metal
reactor and treated with nitrogen at 150.degree. C. overnight.
Next, MeCl (30 mL/min) was flowed through the PdSi bed at
400.degree. C. for 4 h. The products were analyzed by GC and found
to contain Me.sub.2SiCl.sub.2 (57.3% (w/w)), and MeSiCl.sub.3
(42.7% (w/w)). Si conversion was 5.6%.
Example 14
A sample of PdSi (500.0 mg) was loaded into a flow-through, metal
reactor and treated with nitrogen at 150.degree. C. overnight.
Next, MeCl (30 mL/min) was flowed through the PdSi bed at
400.degree. C. for 6 h. The products were analyzed by GC and found
to contain Me.sub.2SiCl.sub.2 (46.5% (w/w)), and MeSiCl.sub.3
(53.5% (w/w)). Si conversion was 8.5%.
Example 15
A sample of grinded PdSi (500.0 mg; particle size <50 micron)
was loaded into a flow-through, metal reactor and treated with
nitrogen at 150.degree. C. overnight. Next, MeCl (30 mL/min) was
flowed through the PdSi bed at 400.degree. C. for 5 h. The products
were analyzed by GC and found to contain MeHSiCl.sub.2 (2.0%(w/w)),
SiCl.sub.4 (10.2% (w/w)), Me.sub.2SiCl.sub.2 (14.8% (w/w)),
MeSiCl.sub.3 (72.3% (w/w)) and (MeO)SiCl.sub.3 (0.5% (w/w)). Si
conversion was 14.0%.
Comparative Example 1
An open-ended, glass tube was loaded with NiSi (0.5 g). The tube
was heated to 330.degree. C. with an aluminum heating block, and
MeBr was then pumped through the tube for 7 h. There were no
organohalosilanes detected by GC-MS in the material collected in a
downstream cold trap at -78.degree. C.
Comparative Example 2
An open-ended, glass tube was loaded with CoSi.sub.2 (0.5 g). The
sample was pretreated with N.sub.2 at 250.degree. C. for 45 min,
and then MeCl (25-40 mL/min) was flowed through the system at
330.degree. C. for 3-5.5 h. No liquids were collected in a
downstream cold trap (-78.degree. C.). There were no
organohalosilanes detected.
Comparative Example 3
An open-ended, glass tube was loaded with CrSi.sub.2 (0.5 g). The
sample was pretreated with N.sub.2 at 250.degree. C. for 45 min,
and MeCl (25-40 mL/min) was then flowed through the system at
330.degree. C. for 3-5.5 h. No liquids were collected in a
downstream cold trap (-78.degree. C.), and no organohalosilanes
were detected by GC-MS.
Comparative Example 4
An open-ended, glass tube was loaded with WSi.sub.2 (0.5 g). The
sample was pretreated with N.sub.2 at 250.degree. C. for 45 min,
and MeCl (25-40 mL/min) was then flowed through the system at
330.degree. C. for 3-5.5 h. No liquids were collected in a
downstream cold trap (-78.degree. C.), and no organohalosilanes
were detected by GC-MS.
Comparative Example 5
An open-ended, glass tube was loaded with TaSi.sub.2 (0.5 g). The
sample was pretreated with N.sub.2 at 250.degree. C. for 45 min,
and MeCl (25-40 mL/min) was then flowed through the system at
330.degree. C. for 3-5.5 h. No liquids were collected in a
downstream cold trap (-78.degree. C.), and no organohalosilanes
were detected by GC-MS.
Comparative Example 6
A thick-wall glass reactor tube was charged with a sample of NiSi
(110 m) and methyl iodide (75 .mu.L) at 23.degree. C. The tube was
evacuated at -196.degree. C., sealed, and then warmed to room
temperature. The tube was kept in an oven and heated at 300.degree.
C. After 5 h, the temperature of the reactor tube was allowed to
reach 23.degree. C. and then was frozen with liquid nitrogen
(-196.degree. C.). Using a triangular file, the tube was cut,
warmed to room temperature, and then a liquid sample was collected
for analysis. A direct liquid sample injection was made on gas
chromatography-mass spectrometry and no organohalosilanes were
detected.
Comparative Example 7
A sample of Pd.sub.9Si.sub.2 (500.0 mg) was loaded into the
flow-through, metal reactor and pretreated with nitrogen at
150.degree. C. overnight. Next, MeCl (30 mL/min) was flowed through
the Pd.sub.9Si.sub.2 bed, and the products evolving at from
400-600.degree. C. were analyzed by GC-MS. No organohalosilanes
were detected. At 600-700.degree. C., evolution of only SiCl.sub.4
was observed.
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